CN112973727A - Catalyst for cyclohexane oxidation, preparation method and application thereof - Google Patents
Catalyst for cyclohexane oxidation, preparation method and application thereof Download PDFInfo
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- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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Abstract
The invention provides a catalyst for cyclohexane oxidation, a preparation method and application thereof. The catalyst is Pd-Co3O4‑CeO2And (c) a complex. By using Pd-Co3O4‑CeO2The compound is used as a catalyst for cyclohexane oxidation, the noble metal Pd can improve the oxidation rate of cyclohexane, and Co3O4Can activate cyclohexane to promote the oxidation reaction of cyclohexane, and has good catalytic effect, and CeO2Also has obvious promotion effect on high-temperature catalytic reaction. By combining Pd, Co and Ce to form Pd-Co3O4‑CeO2The compound has the catalytic characteristics of Pd, Co and Ce, can be used as a composite catalyst for cyclohexane oxidation, and improves the conversion rate of cyclohexane and the selectivity of adipic acid.And the cobalt-based and noble metal catalyst has stable reaction activity and is not easy to generate carbon deposition to cause inactivation, thereby realizing the continuous production of preparing adipic acid by gas phase oxidation of cyclohexane.
Description
Technical Field
The invention relates to the field of catalytic application, in particular to a catalyst for cyclohexane oxidation, a preparation method and application thereof.
Background
Adipic acid is an important chemical raw material. Currently, the industrial production of adipic acid is mainly prepared by the two-step oxidation of cyclohexane: cyclohexane is oxidized in a liquid phase to generate cyclohexanol and cyclohexanone, commonly called KA oil, and then the KA oil is oxidized by nitric acid. The cyclohexane liquid phase oxidation is a free radical process, the reaction is difficult to control, a large amount of strong acid and strong alkali solution is needed for the reaction, the equipment is seriously lost, the environment is also seriously polluted, and the reaction needs to be carried out in a high-pressure kettle, so that potential safety hazards exist. The gas phase oxidation of cyclohexane does not need high-pressure equipment and can be continuously operated, so that the gas phase oxidation of cyclohexane is more and more concerned.
Medina-Valtierra et al chemically vapor deposited Cu2O is deposited on the glass fiber, and the catalyst is used for catalyzing the gas phase oxidation of cyclohexane, the selectivity of the cyclohexanol and the cyclohexanone reaches 60 percent, and the selectivity of the adipic acid reaches 6 percent.
Liuxiu takes molecular sieve loaded metalloporphyrin as a catalyst, the selectivity of cyclohexanol and cyclohexanone reaches 40%, and the main byproduct is valeraldehyde.
In the method for preparing adipic acid by using cyclohexane, high-pressure equipment such as an autoclave is not required, continuous operation can be realized, but the selectivity of cyclohexane gas-phase oxidation is low, and the industrial production requirement cannot be met.
Disclosure of Invention
The invention mainly aims to provide a catalyst for cyclohexane oxidation, a preparation method and application thereof, so as to solve the problem of low selectivity of preparing adipic acid by cyclohexane oxidation in the prior art.
In order to accomplish the above object, an aspect of the present invention provides a catalyst for cyclohexane oxidation, which is Pd-Co3O4-CeO2And (c) a complex.
Furthermore, the mole number of Pd accounts for 0.1-10% of the total mole number of palladium, cobalt and cerium in the catalyst, and the mole number of Co accounts for 10-50% of the total mole number of palladium, cobalt and cerium in the catalyst.
According to another aspect of the present invention, there is also provided a method for preparing the above catalyst, which comprises: dissolving palladium salt, cobalt salt and cerium salt in water, and adding a surfactant to obtain a mixed solution; adding a pH regulator into the mixed solution to regulate the pH to be alkaline, and obtaining a solid precipitate; washing and purifying the solid precipitate, and then preparing into particles; the particles are activated to obtain the catalyst.
Further, the palladium salt is selected from one or more of palladium chloride, palladium nitrate and palladium acetate; the cobalt salt is selected from one or more of cobalt nitrate, cobalt acetate and cobalt acetylacetonate; the cerium salt is selected from one or more of cerium nitrate, cerium acetate and cerium acetylacetonate; preferably, the surfactant is selected from one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tween 20, tween 60 and tween 80.
Further, the pH regulator is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Further, the average particle diameter of the particles is 1 to 10 mm.
Further, characterized in that the activating step comprises: drying at 120 ℃ to constant weight, and then roasting at 400-550 ℃ for 4 h.
According to another aspect of the present invention, there is also provided a method for preparing adipic acid by gas phase oxidation of cyclohexane, comprising: evaporating cyclohexane, and mixing with oxygen and nitrogen to obtain mixed gas; introducing the mixed gas into a reaction device provided with the catalyst, and heating the reaction device to perform oxidation reaction to obtain a reaction product; the reaction product is cooled to obtain cyclohexanol, cyclohexanone and adipic acid.
Further, in the mixing process, cyclohexane, oxygen and nitrogen are heated, and the heating temperature is 35-120 ℃.
Further, the molar ratio of nitrogen to oxygen during the mixing process is n1: 1, wherein 0 < n1<30, preferably 0.1 < n1<2; the ratio of the total mole number of nitrogen and oxygen to the mole number of cyclohexane is n2: 1, wherein, 0<n2<100, preferably, 2 < n2<8。
Further, the temperature in the oxidation reaction process is 220-400 ℃.
Further, the process of cooling the reaction product comprises: carrying out primary cooling on the reaction product at the temperature of 180-220 ℃ to obtain adipic acid, cyclohexane, low-boiling-point byproducts and residual gas; and carrying out secondary cooling on the residual gas at the temperature of 0-120 ℃ to obtain cyclohexanol and cyclohexanone.
The technical scheme of the invention adopts Pd-Co3O4-CeO2The compound is used as a catalyst, wherein the noble metal Pd can improve the oxidation rate of cyclohexane, Co3O4Can activate cyclohexane to promote the oxidation reaction of cyclohexane, and has good catalytic effect, and CeO2Also has obvious promotion effect on high-temperature catalytic reaction. By combining Pd, Co and Ce to form Pd-Co3O4-CeO2Composite to obtain catalyst having Pd, Co and CeThe catalyst has the advantages of high conversion rate of cyclohexane and high selectivity of adipic acid, and can be used as a composite catalyst for cyclohexane oxidation. And the cobalt-based and noble metal catalyst has stable reaction activity and is not easy to generate carbon deposition to cause inactivation, thereby realizing the continuous production of preparing adipic acid by gas phase oxidation of cyclohexane.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic flow diagram for the gas phase oxidation of cyclohexane to adipic acid according to one embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background, the prior art suffers from the problem of low selectivity in the oxidation of cyclohexane to adipic acid. In order to solve the technical problem, the invention provides a catalyst for cyclohexane oxidation, which is Pd-Co3O4-CeO2And (c) a complex.
According to the scheme provided by the application, Pd-Co is adopted3O4-CeO2The compound is used as a catalyst, wherein the noble metal Pd can improve the oxidation rate of cyclohexane, Co3O4Can activate cyclohexane to promote the oxidation reaction of cyclohexane, and has good catalytic effect, and CeO2Also has obvious promotion effect on high-temperature catalytic reaction. By combining Pd, Co and Ce to form Pd-Co3O4-CeO2The compound has the catalytic characteristics of Pd, Co and Ce, can be used as a composite catalyst for cyclohexane oxidation, and improves the conversion rate of cyclohexane and the selectivity of adipic acid. Wherein, the cobalt-based and noble metal catalyst has stable reaction activity and is not easy to generate carbon deposition to cause inactivation, thereby realizing cyclohexaneContinuous production of adipic acid by gas phase oxidation.
In a preferred embodiment, the mole number of Pd is 0.1-10% of the total mole number of Pd, Co and Ce in the catalyst, and the mole number of Co is 10-50% of the total mole number of Pd, Co and Ce in the catalyst. The different catalytic characteristics of Pd, Co and Ce are coordinated by adjusting the proportion of Pd, Co and Ce, wherein the proportion of Pd pertinently reduces the reaction temperature of cyclohexane gas phase oxidation, and the proportion of Co and Ce respectively plays a role in activating cyclohexane and catalyzing cyclohexane oxidation, thereby improving the cyclohexane conversion rate, reducing the generation amount of byproducts and simultaneously improving the selectivity of adipic acid.
In an exemplary embodiment, the present application provides a method of making any of the above catalysts, the method comprising: firstly, dissolving palladium salt, cobalt salt and cerium salt in water, and adding a surfactant to obtain a mixed solution; then adding a pH regulator into the mixed solution to regulate the pH to be alkaline, and obtaining a solid precipitate; washing and purifying the solid precipitate, and then preparing into particles; finally, activating the particles to obtain the catalyst.
According to the method provided by the application, firstly, palladium salt, cobalt salt and cerium salt are dissolved in water, and in order to promote dissolution, surfactant is added simultaneously, so that the three metal salts are fully and uniformly mixed to form a mixed solution. And then the pH of the mixed solution is adjusted to be alkaline, so that the composite composed of the three metals is precipitated. In order to improve the catalytic property of the compound, the compound precipitate is washed and purified and then is made into particles. Finally, activating the particles to obtain the catalyst for oxidizing cyclohexane. By adopting the scheme, the process flow is simple and is suitable for industrial production.
In a preferred embodiment, the palladium salt is selected from one or more of palladium chloride, palladium nitrate and palladium acetate; the cobalt salt is selected from one or more of cobalt nitrate, cobalt acetate and cobalt acetylacetonate; the soluble cerium salt is selected from one or more of cerium nitrate, cerium acetate and cerium acetylacetonate; preferably, the surfactant is selected from one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tween 20, tween 60 and tween 80. The palladium salt, cobalt salt, cerium salt and surfactant in the present application include, but are not limited to, the above listed species, but by using the above species, not only the catalytic effect of cyclohexane oxidation can be further promoted, but also the selectivity of adipic acid can be improved, and the raw materials are easily available and low in cost. In addition, the addition of the surfactant can better disperse the catalyst components, and is beneficial to obtaining a catalyst with more proper specific surface area.
In a preferred embodiment, the pH adjusting agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate. The pH regulator includes, but is not limited to, the above-mentioned ones, but the use of the above-mentioned ones is less costly and more suitable for industrial use.
In a preferred embodiment, the particles have an average particle size of 1 to 10 mm. The average particle size of the prepared particles is not limited to the range, but the particle size in the range can obtain larger total specific surface area, and when the catalyst is used for catalyzing cyclohexane oxidation, the same amount of the catalyst can obtain larger contact area with cyclohexane, so that the catalytic effect of cyclohexane oxidation is improved, and the conversion rate of cyclohexane is improved.
In a preferred embodiment, the activating step further comprises: drying at 120 ℃ to constant weight, and then roasting at 400-550 ℃ for 4 h. After the compound is activated, the catalytic effect of the catalyst can be further improved, and the selectivity of adipic acid is improved. During the activation process, the added surfactant is carbonized and burnt to generate pores.
In another exemplary embodiment, the present application provides a method for preparing adipic acid by gas phase oxidation of cyclohexane, as shown in fig. 1, the method comprising: firstly, gasifying cyclohexane through a gasifier, and then introducing the gasified cyclohexane, oxygen and nitrogen into a mixer for mixing to obtain mixed gas; introducing mixed gas into a double-layer jacketed pipe type reactor containing any one of the catalysts, filling the catalyst into an inner pipe, and heating for oxidation reaction to obtain a reaction product; the reaction product is cooled to obtain cyclohexanol, cyclohexanone and adipic acid.
According to the method provided by the application, cyclohexane is firstly vaporized and mixed with oxygen and nitrogen, and then the oxidation reaction is carried out under the action of the catalyst to prepare adipic acid. As more strong base and strong acid are needed in the liquid-phase oxidation process of cyclohexane, the equipment is seriously lost, high-pressure equipment is needed, great danger exists, and continuous production is difficult. The gas-phase oxidation of cyclohexane is adopted, so that the defect of liquid-phase oxidation is avoided, the conversion rate of cyclohexane and the selectivity of adipic acid are improved, and meanwhile, the continuous operation can be realized, and the method is suitable for industrial production.
In a preferred embodiment, in the mixing process, the mixer is heatable, and cyclohexane, oxygen and nitrogen are heated, wherein the heating temperature is 35-120 ℃. By preheating cyclohexane, oxygen and nitrogen in the mixing process, the full mixing of the three gases is promoted, and meanwhile, the preparation is made for the oxidation reaction of the mixed gas, so that the generation of byproducts is reduced.
In a preferred embodiment, cyclohexane, oxygen and nitrogen are mixed via separate, measurable lines via a mass flow controller, wherein cyclohexane is metered by a metering pump, vaporized by a vaporizer and then mixed with oxygen and nitrogen in a mixer, wherein the molar ratio of nitrogen to oxygen is n1: 1, wherein 0 < n1<30, preferably 0.1 < n1<2; the ratio of the total mole number of nitrogen and oxygen to the mole number of cyclohexane is n2: 1, wherein, 0<n2<100, preferably, 2 < n2<8。
Cyclohexane, oxygen and nitrogen include but are not limited to the above range, and the proportion of nitrogen and oxygen in the above range can ensure that the whole oxidation reaction is under the protection of nitrogen, and the generation of oxidation byproducts is reduced. The ratio of the total number of moles of nitrogen to oxygen to the number of moles of cyclohexane can increase the conversion of cyclohexane and promote the production of adipic acid.
In a preferred embodiment, the jacket is heated by heat conduction oil or molten salt, the temperature inside the reactor is measured by a thermocouple, 1-4 temperature measuring points can be selected, the two ends of the reactor are provided with detection ports, an oxygen sensing detector or a hydrocarbon concentration detector can be connected on line, and the temperature in the oxidation reaction process is 220-400 ℃. Due to the action of the catalyst, the oxidation reaction is carried out within the temperature range, so that the full progress of the cyclohexane oxidation reaction can be ensured, the energy consumption can be reduced, and the resources can be saved.
In a preferred embodiment, the cooling of the reaction product comprises: carrying out primary cooling on the reaction product at the temperature of 180-220 ℃ by adopting a high-temperature cold trap to obtain condensed adipic acid, cyclohexane, low-boiling-point byproducts (carbon dioxide and water with small amount) and residual gas; and then, carrying out secondary cooling on the residual gas at the temperature of 2-120 ℃ by adopting a low-temperature cold trap to obtain cyclohexanol and cyclohexanone. And the separation of adipic acid, cyclohexanone and cyclohexanol which are products of the cyclohexane oxidation reaction is realized by adopting step-by-step cooling, so that the selectivity of the adipic acid is further improved.
The present invention is described in further detail below with reference to specific examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1
Catalyst preparation 5 mmol of palladium sulfate, 30 mmol of cobalt acetate (ferric nitrate, manganese acetate) and 65 mmol of cerium nitrate were dissolved in 1 liter of distilled water, and 20 mmol of cetyltrimethylammonium bromide was added thereto and stirred to prepare a solution. With vigorous stirring, a 1M NaOH solution was added to a pH of 10. After the addition of the base was complete, stirring was continued for 4 h. Filtering under reduced pressure, collecting colloid, and oven drying at 120 deg.C to constant weight. Then roasting at the high temperature of 500 ℃ for 4h to obtain the three-way catalyst.
Taking 10g of the catalyst prepared by the preparation method, fixing the catalyst in a tubular reactor with the diameter of 2cm, and simultaneously introducing vaporized cyclohexane, oxygen and nitrogen from the upper part of a mixer, wherein the heating temperature of the mixer is 80 ℃ to obtain mixed gas, wherein N is2:O2＝1，(N2:O2)：C6H12(cyclohexane) ═ 5. Then introducing the mixed gas into a reactor, keeping the temperature of the reactor at 300 ℃, stopping the reaction after continuously reacting for 6 hours,and then sequentially condensing the obtained reaction product through a high-temperature cold trap and a low-temperature cold trap, wherein the cooling temperature of the high-temperature cold trap is 190 ℃ to obtain adipic acid, and the cooling temperature of the low-temperature cold trap is 80 ℃ to obtain cyclohexanol and cyclohexanone. The cooling liquid was analyzed, and the results are shown in Table 1.
Example 2
In contrast to example 1, the heating temperature in the mixer was 120 ℃, the reactor temperature was 400 ℃, and N was2:O2＝0.1。
Example 3
In contrast to example 1, the heating temperature in the mixer was 35 ℃ and N2:O2＝0.2。
Example 4
In contrast to example 1, N2:O2The cooling temperature of the high-temperature cold trap is 210 ℃ and the cooling temperature of the low-temperature cold trap is 120 ℃.
Example 5
In contrast to example 1, N2:O2The cooling temperature of the high-temperature cold trap is 180 ℃, and the cooling temperature of the low-temperature cold trap is 25 ℃.
TABLE 1 analysis of the results of cyclohexane oxidation
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by using Pd-Co3O4-CeO2The compound is used as a catalyst, wherein the noble metal Pd can improve the oxidation rate of cyclohexane, Co3O4Can activate cyclohexane to promote the oxidation reaction of cyclohexane, and has good catalytic effect, and CeO2Also has obvious promotion effect on high-temperature catalytic reaction. Formed by combining Pd, Co and CePd-Co3O4-CeO2The compound has the catalytic characteristics of Pd, Co and Ce, can be used as a composite catalyst for cyclohexane oxidation, and improves the conversion rate of cyclohexane and the selectivity of adipic acid. The cobalt-based and noble metal catalyst has stable reaction activity and is not easy to generate carbon deposition to cause inactivation, thereby realizing the continuous production of preparing adipic acid by gas phase oxidation of cyclohexane. Under the action of the catalyst, cyclohexane is first vaporized and mixed with oxygen and nitrogen to produce adipic acid through oxidation reaction. As more strong base and strong acid are needed in the liquid-phase oxidation process of cyclohexane, the equipment is seriously lost, high-pressure equipment is needed, great danger exists, and continuous production is difficult. The gas-phase oxidation of cyclohexane is adopted, so that the defect of liquid-phase oxidation is avoided, the conversion rate of cyclohexane and the selectivity of adipic acid are improved, and meanwhile, the continuous operation can be realized, and the method is suitable for industrial production.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The catalyst for cyclohexane oxidation is characterized in that the catalyst is Pd-Co3O4-CeO2And (c) a complex.
2. The catalyst of claim 1, wherein the mole of Pd is 0.1-10% of the total mole of Pd, Co and Ce in the catalyst, and the mole of Co is 10-50% of the total mole of Pd, Co and Ce in the catalyst.
3. A method for preparing the catalyst of claim 1 or 2, comprising:
dissolving palladium salt, cobalt salt and cerium salt in water, and adding a surfactant to obtain a mixed solution;
adding a pH regulator into the mixed solution to regulate the pH to be alkaline, and obtaining a solid precipitate;
washing and purifying the solid precipitate, and then preparing into particles;
activating the particles to obtain the catalyst.
4. The method according to claim 3, wherein the palladium salt is selected from one or more of palladium chloride, palladium nitrate and palladium acetate; the cobalt salt is selected from one or more of cobalt nitrate, cobalt acetate and cobalt acetylacetonate; the cerium salt is selected from one or more of cerium nitrate, cerium acetate and cerium acetylacetonate; preferably, the surfactant is selected from one or more of octadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, tween 20, tween 60 and tween 80.
5. The method according to claim 4, wherein the pH adjuster is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate.
6. The method according to claim 5, wherein the average particle diameter of the particles is 1 to 10 mm.
7. The method for preparing according to any one of claims 3 to 6, wherein the activating step comprises: drying at 120 ℃ to constant weight, and then roasting at 400-550 ℃ for 4 h.
8. A method for preparing adipic acid by gas phase oxidation of cyclohexane, which comprises the following steps:
evaporating cyclohexane, and mixing with oxygen and nitrogen to obtain mixed gas;
introducing the mixed gas into a reaction device provided with the catalyst of any one of claims 1 to 7, and heating the reaction device to perform oxidation reaction to obtain a reaction product;
cooling the reaction product to obtain cyclohexanol, cyclohexanone and the adipic acid.
9. The method according to claim 8, wherein the cyclohexane, the oxygen, and the nitrogen are heated at a temperature of 35 to 120 ℃ during the mixing.
10. The method of claim 9, wherein the molar ratio of the nitrogen gas to the oxygen gas during the mixing is n1: 1, wherein 0 < n1<30, preferably 0.1 < n1<2; the ratio of the total number of moles of the nitrogen to the oxygen to the number of moles of the cyclohexane is n2: 1, wherein, 0<n2<100, preferably, 2 < n2<8。
11. The method according to claim 10, wherein the temperature during the oxidation reaction is 220 to 400 ℃.
12. The method of any one of claims 8 to 11, wherein cooling the reaction product comprises:
carrying out primary cooling on the reaction product at the temperature of 180-220 ℃ to obtain the adipic acid, cyclohexane, low-boiling-point byproducts and residual gas;
and carrying out secondary cooling on the residual gas at the temperature of 0-120 ℃ to obtain the cyclohexanol and the cyclohexanone.
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|---|---|---|---|---|
| CN115608370A (en) * | 2022-10-13 | 2023-01-17 | 化学与精细化工广东省实验室 | Catalyst for preparing adipic acid by one-step oxidation of cyclohexane and preparation method thereof |
| CN115608370B (en) * | 2022-10-13 | 2023-11-03 | 化学与精细化工广东省实验室 | Catalyst for preparing adipic acid by cyclohexane one-step oxidation and preparation method thereof |
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| CN112973727B (en) | 2023-07-25 |
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